Production and treatment of textile and other materials made of or containing cellulose derivatives



Patented Mar. 6, 1934 omrso STATES PATENT OFFICE Henry Dreyfus, London, England No Drawing. Application May 8, 1930, Serial No. 450,871. In Great Britain May 31, 1929 14 Claims.

This invention relates to the production of artificial filaments, threads, ribbons, films and the like from solutions containing cellulose derivatives and also relates to the treatment of artiflcial filaments, threads, ribbons, films, fabrics or other materials made of or containing cellulose derivatives. The term cellulose derivatives is used in this specification as including only stable or relatively stable derivatives of cellulose, and particularly the carboxylic acid esters and ethers of cellulose, so that viscose is excluded.

According to the present invention materials made of or containing cellulose derivatives, for example filaments, threads, ribbons, films or the li are treated with organo-mineral acids, for example sulphonic acids, or with strong aqueous or other solutions thereof. The term organomineral acids is used as denoting the derivatives theoretically obtainable by replacing one or more hydroxy groups of a dior poly-basic mineral acid with one or more aryl, alkyl or aralkyl or other or t .io radicles, one or more hydroxy groups still remaining therein.

The treatment in general results in an improved strength and/or elasticity of the materials and/or in a modification of the surface thereof, and particularly a modification in lustre.

The treatment with the sulphonic acids or other organo-mineral acids may be efiected in any desired manner. In the case of treated finished artificial fibres or materials made of or containing cellulose esters or others, the treatment may be applied to the materials under tension or so as to allow the materials to shrink. Artificial filaments, threads, ribbons or the like ma r further be treated by means of the sulphonic acids or other organo-mineral acids continuously with their production by wet or dry spinning processes. For example cellulose acetate filaments on coming out of a dry-spinning cell or chamber may be carried through a bath containing one or more of the organo-mineral acids, or again cellulose acetate or other artificial filaments on emergence from the coagulating bath may be carried directly into a second bath containing such a reagent.

The present invention however is productive of the most useful results when the organomineral acids are employed directly as coagulating baths for solutions of cellulose esters or ethers.

In the case of using the organo-mineral acids in the coagulating bath for the cellulose derivatives, I find that very good results indeed may be obtained by applying a stretch to the filaments or other products during their passage through the coagulating bath, or after emergence from the coagulating bath, for example between the coagulating bath and the winding device. The application of a tension or stretch to the materials during or after treatment with the organo-mineral acids is not however limited in its application to the case in which the organomineral acid constitutes the coagulating bath, since tension or stretch may also be used in the v case of treating already finished products with the organo-mineral acids.

Whatever method is employed the materials after treatment are preferably allowed to remain in contact with the sulphonic acids or other organo-mineral acids for a short time, after which they may, if necessary, be washed to remove the acids and avoid any destruction consequent upon prolonged contact of the materials therewith. For example they may be washed with water alone or with water containing alkali 7 or other base.

The acids or their concentrations should be so chosen or adjusted as to avoid any substantial deleterious efiect upon the materials under treatment. For example substantial hydrolysis of cellulose ester material is preferably avoided. The coagulating bath in the case of wet spinning or any other bath containing the sulphonic acids or other organo-mineral acids may be maintained at atmospheric temperature or at temperatures below atmospheric, for example 0 to 10 C., or at temperatures somewhat above atmospheric temperature.

As examples of suitable acids the following may be mentionedz-methyl sulphonic acid, ethylene sulphonic acid, propyl 1.2 or 1.3 di-sulphonic acid, sulphoacetio acid, sulphosuccinic acid, ethanol sulphonic acid, benzyl sulphonic acid, benzene sulphonic acid, phenol sulphonic acids, phenol di-sulphonic acids, sulpho-salicylic acid, sulpho-phthalic acid, naphthalene sulphonic acids, naphthol sulphonic acids, dimethyl phosphinic acid, nitrophenyl phosphinic acid, etc. Substances exerting a solvent or solute action on the cellulose derivative may be present in the baths in addition to the acids. Alternatively or in addition one or more substituent groups which induce solvent or solute power for the cellulose derivative, for example hydroxy or amino groups may be present in the organo-mineral acids.

The sulphonic acids or other strong organomineral acids may be employed in relatively concentrated aqueous solution, for example aqueous solutions of more than 20% strength and particularly 30 to 50% strength or more, or they may 1h be employed in solution in organic solvents, for example alcohols, if soluble therein, or in mixed aqueous organic solvents, for example aqueous alcohol.

The following examples show the best methods known to me for carrying the invention into effeet but they are not to be regarded as limiting the invention in any way:-

Example 1 A acetone solution of cellulose acetate is spun at a speed of metres per minute into a bath consisting of a 40% aqueous solution of sulpho-acetic acid, the length of immersion of the filaments in the bath being about 5 to 8 inches. On emergence from the bath the yarn is passed over a guide and is then wound on a bobbin running in a bath of water or of dilute ammonia or continuously sprayed with water or dilute ammonia.

Example 2 A 20% acetone solution of cellulose acetate is spun as described in Example 1 into a coagulating bath consisting of a solution of ethylene sulphonic acid. After emergence from the coagulating bath the yarn is passed over a feed roller and thence into a bath containing dilute ammonia, after which it may be wound on bobbins or twisted or hanked. The hanks may be washed and dried under a slight tension.

Example 3 A 25% acetone solution of cellulose acetate is spun into a bath consisting of a 25% aqueous solution of diacetone alcohol. After emergence from the bath the yarn is passed round a feed roller rotating at a peripheral speed of 25 metres per minute and is then passed into a second bath consisting of a aqueous solution of sulphoacetic acid, the length of immersion being 5 to 8 inches. The yarn is thereafter passed round a second feed roller rotating at a peripheral speed of 30 metres per minute, after which the yarn is washed and wound or twisted and wound as described in Example 2.

Example 4 Cellulose acetate filaments or threads are passed from a bobbin or package or direct from a dry or wet spinning apparatus at a speed of 25 to 35 metres per minute through a bath consisting of a aqueous solution of methyl sulphonic acid, after which they are passed round a feed roller running at a sufiicient peripheral speed to maintain a tension therein or to produce an elongation, say of 10%. The filaments or threads are thereafter washed and treated as described in the preceding examples.

In a similar manner cellulose acetate may be spun into or treated with other organo-mineral acids, for example the various sulphonic acids or phosphinic acids mentioned above, and in addition other cellulose derivatives, for example cellu lose formate, cellulose propionate, cellulose butyrate, or methyl ethyl or benzyl cellulose may be treated. Furthermore materials containing any of these cellulose derivatives in admixture with other fibres, for example cotton, which are not deleteriously affected by the sulphonic or other organo-mineral acids, may likewise be subjected to similar treatments.

What I claim and desire to secure by Letters Patent is:-

1. Process for the manufacture of artificial materials comprising treating materials comprising derivatives of cellulose selected from the group consisting of carboxylic acid esters of cellulose and cellulose ethers with organo-mineral acids of concentration at least 30%.

2. Process for the production of materials comprising derivatives of cellulose selected from the group consisting of carboxylic acid esters of cellulose and cellulose ethers, comprising extruding solutions containing said derivatives into organomineral acids of concentration at least 30%.

3. Process for the manufacture of artificial materials comprising treating materials comprising cellulose acetate with organo-mineral acids of concentration at least 30%.

4. Process for the production of materials comprising cellulose acetate, comprising extruding solutions containing cellulose acetate into organomineral acids of concentration at least 30%.

5. Process for the production of materials comprising cellulose acetate, comprising extruding solutions containing cellulose acetate into organomineral acids of concentration at least 6. Process for the manufacture of artificial materials comprising treating materials comprising cellulose acetate with organo-mineral acids of concentration at least 50%.

7. Process for the manufacture of artificial materials comprising treating materials comprising derivatives of cellulose selected from the group consisting of carboxylic acid esters of cellulose and cellulose ethers with organo-mineral acids of concentration at least 30% and subjecting them to tension.

8. Process for the production of materials comprising derivatives of cellulose selected from the group consisting of carboxylic acid esters of cellulose and cellulose ethers, comprising extruding solutions containing said derivatives into organomineral acids of concentration at least 30%, the

process being effected in such a manner that the l materials are subjected to tension.

9. Process for the manufacture of artificial materials comprising treating materials comprising derivatives of cellulose selected from the group consisting of carboxylic acid esters of cellulose and cellulose ethers with organo-mineral acids of concentration at least 30% and stretching them.

10. Process for the production of materials comprising derivatives of cellulose selected from the group consisting of carboxylic acid esters of i cellulose and cellulose ethers, comprising extruding solutions containing said derivatives into organo-mineral acids of concentration at least 30%, the process being effected in such a manner that the materials are stretched.

11. Process for the manufacture of artificial materials comprising treating materials comprising cellulose acetate with aliphatic sulphonic acids of concentration at least 30%.

12. Process for the production of materials comprising cellulose acetate, comprising extruding solutions containing cellulose acetate into aliphatic sulphonic acids of concentration at least 30%.

13. Process for the manufacture of artificial materials comprising treating materials comprising cellulose acetate with sulpho carboxylic acids of concentration at least 30%.

14. Process for the production of materials comprising cellulose acetate, comprising extruding solutions containing cellulose acetate into sulpho carboxylic acids of concentration at least 30%.

HENRY DREYFUS. 

